Soluble interpolymers of a poly-2-alkenyl ester, vinylidene chloride, and a monounsaturated 2-alkenyl compound



where products of decreased flammability are de sired, although such materials are somewhat inferior to the interpolymers of the 2-alkenyl alcohols, ethers and carboxylic acid esters in regard to their resistance to discoloration at high temperatures. For optimum resistance to wetting and attack by hydrophilic solvents, the interpolymers of the 2-alkenyl ethers of non-enic monohydric alcohols are preferred, although in many cases the interpolymers of the Z-alkenyl esters of non-enic monocarboxylic acids have proven nearly equivalent in this respect. Both the 2-alkenyl mono-ethers and the carboxylic mono-ester are likewise useful in endowing the resulting copolymers with improved flexibility, and this efiect can be enhanced by the use of the 2-alkenyl ethers and esters of long chain alcohols and carboxylic acids respectively. The interpolymers of the 2-alkenyl mono-esters tend to cure to a solventand heat-resistant state more slowly and under more stringent conditions than do the interpolymers of the 2-alkenyl mono-ethers.

I have found that the presence of as little as 0.2 mole of the interpolymeriza'ble mono-Z-alkenyl compound (per mole of the poly-Z-alkenyl ester) in the initial reactant mixture is suificient to effect a marked increase in the conversion of the poly-2-alkeny1 ester and copolymerizable monoolefinic compound to the soluble, interpolymeric form, and that the major proportion of these monomers is converted to soluble interpolymer when about 3.5-5 moles of the mono-2- alkenyl compound are initially present, and even higher conversions are attained as the amount of the latter is further increased, e. g., to 7-10 moles. Generally there is no particular advantage in using more than moles of the additional mono-z-alkenyl compound.

Suitable poly-2-alkenyl esters (A) for use in my invention are derived from any polybasic acid and any of the 2-alkenyl alcohols, including allyl, Z-methallyl, Z-ethallyl,2-chloroallyl, 2-hydroxymethyl) allyl, 2- (chloromethyl) allyl, tiglyl, crotyl, 4-chlorocr0tyl, and cinna-myl alcohols, of which those containing a terminal methylene group are preferred, e. g., allyl and methallyl alcohols. Although such poly-2-alkenyl esters of a wide variety of polybasic acids are operable in my invention, they differ to a considerable degree in their relative reactivities as well as in the character of the resulting products. Thus, for example, the poly-Z-alkenyl esters of olefinic polycarboxylic acids tend to interpolymerize more rapidly by my method than the corresponding poly-2-alkenyl esters of saturated polycarboxylic acids, and the resulting polymeric products are generally of higher molecular weight. In the former class, the poly-2-alkenyl esters of alpha-olefim'c polycarboxylic acids are preferred, e. g., diallyl fuma rate, diallyl maleate, dimethallyl itaconate, di-Z- chloroallyl itaconate, diallyl mesaconate, dimethallyl citraconate, and triallyl aconitate. Of these, the di-2-alkenyl fumarates are particularly efiicacious in view of their cheapness, their speed of reaction, the high yields of soluble interpolymers obtained therefrom, and the character of the solventand heat-resistant products resulting from the curing of the interpolymers. The di-2-alkenyl maleates yield interpolymers which tend to yellow somewhat upon aging. The di-2-alkenyl citraconates and tri-2-alkenyl aconitates are somewhat less reactive in my interpolymerization reactions, and the latter likewise yield a markedly softer type of resin.

The poly-Z-alkenyl esters of the non-enic poly- 4 carboxylic acids are useful in my invention, however, particularly when the copolymerizable monoolefinic compound employed therewith is a derivative of an olefinic acid, e. g., an acrylic or fumaric ester. Exemplary of such poly-2-a1kenyl esters are diallyl oxalate, diallyl malonate, diallyl alpha-methylmalonate, diallyl succinate, dimethallyl glutarate, di-Z-chlorallyl adipate, diallyl sebacate, diallyl azelaate, dimethallyl suberate, diallyl phthalate and triallyl carballylate. In this class, the po1y-2-alkenyl esters of the shorterchain acids, e. g., diallyl oxalate and dimethallyl phthalate, tend to yield interpolymers capable of being cured to hard, solvent-resistant products, whereas more flexible products are obtained from the interpolymers of the poly-2-alkenyl esters of the longer chain acids, e. g., diallyl suberate.

Another useful class of poly-2-alkenyl esters are those derived from inorganic polybasic acids. e. g., diallyl carbonate and dimethallyl sulfate, and particularly those derived from the triand tetravalent inorganic acids, e. g., triallyl phosphate, tetraallyl silicate, tetramethallyl stannate and tetraallyl titanate. The latter group find use, according to my invention, in the preparation of the interpolymers which are useful as bases for baking enamels and other non-flammable plastic objects capable of withstanding high temperatures. Like the preceding class, these poly-2-alkenyl esters 'interpolymerize more readily and yield the most satisfactory products when the copolymerizable monoolefinic compound employed therewith is an olefinic acid derivative, e. g., maleimide, acrylamide, diethyl fumarate.

Of the wide variety of copolymerizable monoolefinic compounds (B) which are operable in my invention, a particularly suitable class are those of the formula RR'C=CR"R"' in which the vinyl group is in every case linked to an exocyclic atom, and wherein R may be hydrogen, fluorine or methyl; B may be hydrogen, fluorine, carboxyl, or a group hydrolyzable to carboxyl including carboalkoxy (e. g., carbomethoxy, carboethoxy and carbohexoxy), carboaryloxy (e. g., carbophenoxy and carbotolyloxy), carbaralkoxy (e. g., carbobenzyloxy), carbamyl, N-alkylcarbamyl (e. g., N-methylcarbamyl), N-arylcarbamyl (e. g., N-phenylcarbamyl), and carbonitrilo; R may be hydrogen, lower alkyl (e. g., methyl, ethyl), chlorine, fluorine, carboxyl, or a group hydrolyzable to carboxyl (as defined above); R may be hydrogen, methyl, chlorine, fluorine, carboxyl, a group hydrolyzable to carboxyl, alkoxy (e. g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, amyloxy, hexoxy, heptoxy, octoxy, nonoxy and decoxy) aryloXy (e. g., phenoxy, tolyloxy, naphthoxy, p-chlorophenoxy, and p-methoxyphenoxy), aralkoxy (e. g., benzyloxy), acyloxy where the acyl group is devoid of olefinic and acetylenic unsaturation (e. g., acetoxy, propionoxy, butyroxy and benzoyloxy), acyl as previously defined (e. g., acetyl, propionyl, isobutyryl and benzoyl) and R' may additionally be carboxyl or a group hydrolyzable to carboxyl when R" is carboxyl or a related group; and R' may together with R comprise a dicarbanhydro group (CO-OCO-), or a dicarboimide group (-CONR-CO-), where R is hydrogen, alkyl (e. g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl and decyl) aryl (e. g., phenyl, tolyl, xylyl, xenyl and naphthyl) or aralkyl (e. g., benzyl, beta-'phenethyl) Of the wide variety of such copolymerizable monoolefinic compounds which I may use in my lbenzyl ethyl fumarate, b

v i n. ,rirefe .tqimpl the: wis ih cause of the s e rpr pert esof, thepr duq and because of the; easeand convenience with which the copolymerization; can be 1 carried out,

as well as for reasons of economy,- etc.: v

v 1. The ,propenoic esters of thenon ol eiinic monohydric alcohols, suchmethyl acrylate, methyl methacrylata'butyl acrylate, butyl methacrylate, octyl 'acrylate, beta-'chloroethyl acrylate, benzyl 'acrylate, phenyl--acrylate,f1'etc. Of these, the lower alkyl acrylatesand-methacrylates are especially preferred.

2. Th al -1 efi,nic. olycarh ylic. ac est f the nrq efln e .m no dri altohele ,such as diethyl furnarate, bis (b ta-chloro hyl) fumarate, dibutyl rumar te, rg men -3,

marate, etc., dimethyl itaconate, diethyl 'ita'conate, dihexyl itaconate, dr-cy'emh'exylitacbnate, bis-(beta-phenylethyl) itaconate, dioctyl itaconate, bis-beta-chloroethyl itaconate, etc., as well as the corresponding esters of mesaconic, citraconic, and aconitic acids. Of" these, the

lower alkyl fumaric and itaconic esters are especially preferred. 3. The vinyl esters of the non olennic monocarboxylic acids, such as? vinyl acetate, vinyl .chloroacetate, vinyl butyrate, 'vinyl enzene, vinyl phenylacetate, vinyltrichloroacetate, etc.

Vinyl acetate, propionate "and"biityrate "are especially preferred.

,4. Isobutylene. v p

5. Vinyl chloride, especially when the third,

' interpolymerizable alkehyl' eanipoima' is a 2- alkenyl chloride. l

6. vinylidene chloride, especially when the third, interpolymerizable 'alkenyl' compound is" a 2-alkenyl chloride.

Further examples of prferredimcncolefinic compounds are acrylamide', N-methylacrylamide,'

acrylonitrile, methacrylonitrile, jfumaronitrile, maleimide, N -butylmaleimide, vinyl n'-butyl ether, vinyl hexyl ether, vinyl phenyl'ether," and vinyl benzyl ether.

By the appropriate choice of'copolyfiierizable monoolefinic compound, numerous V variations in the properties of the resulting soluble, unsaturated interpolymers can be attained. -Thus ,'for

example, the interpolyniie'rization -of-" apoly-2- "alkenyl ester and a 2alkenyl'compound with iso- 'butylene yields resins ofimprovedcompatibility with cheap hydrocarbonlsolvents, an-important factor in the formulationof'eohifiircial surface coatings. Copolymerizaticn *with halogenated monoolefinic compounds such as vinyl chloride for vinylidene chloride yieldspolymeric' materials of increased fiame-resistance and--oiten of greater hardness. The latter propertycan' also "be enhanced by copolymerization" withblefinic acid nitriles, amides and"'imides, e. g., acrylonitrile and methacrylamide. bn'th'othei' hand,

softer and mm-flexible Pi euq s'szae' eual rb obtained by the copolymerization with olefinic acid esters of nonenic monohydric'al'coliols, such as the acrylates, methacryla tes;maleates, furnarates, itaconates, mesaconates andfaconitates, particularly such esters derived from" alcohols containing a chain of two or more carbon atoms,- e. g., ethanol, n -butanol,2 etliylhexahol and octanol. I v 1 H M In the*practice of my*invention the-polyhalkenyl ester (A) or mixture of such esters is heated at 25 to 120 C. with from 0.1 to 8.0, prefvalents p: a copoly- "asdefinedabove; or mixture of such ch'mpounds,

and with from 0.2 {to 15;0, prererab1y 02-1010,

pl'oyed 24S My interpelyiiferiz'ation re'a'ctiorr is proirfoted by the presence-of free-radicals, ncurs g those obtained by the thermal decompcsiticnwnperoxides, e. g., organic peroxides such as acetyl peroxide, benzoyl peroxide, cumene hydroperoxide,

and tertiary -b utyl hyarbp'e'foxiae. Siichfpromoters are usually'employed in amounts of from 0.1'to 20.0%,m'ainly from 0.1""tc*5'.'0'%; by weight of the reactant mixtureand-may-beaddedeither at the beginning, j or incrementally throughout t e reaction The rime hqdis"Q tbn' rable when the reaction time exceeds' 36ho firs u n... The course of the reaction can be followed by m u i t increasing inte ity O f 'thei' eaction mixturepand the'product can be isolated therefrom by precipitation througlifaddition of a non-solvent, e. g.,-n-hexane or diethyl ether,

or by removal of; any unreacted starting materials by preferential extraction or distillation. Although it isunnecessary for most; commercial applications, my interpolymers can "be further f purified, as for j analytical fpurposes;' by"solution in a minimum volume of solvent and-fprecipitation by dilutionwith an'ex'cess'of n li'ex'ane' or diethyl ether.

My new interpolyiners can" be employed in the solid form as'thermosetting molding powders for the preparation of various objects'including rods,

blocks and sheets. Alternatively theyfcan be dissolved inappropriate solvents forus as coatin impregnating and laminating compositions. For

such purposes, the crude" interpolymerization' reaction mixtures can themselves be employed by dilutionwith a suitable 'high boilingf solvejnt and subsequent removal {of j any unreacted 2-a1kenyl compound, as by distillation. Alternatively my interpolymersfcan'be' dissolved inliqu'id, copolymerizable ethylenic 'compo'un(is,- e.' gn phen'yl acrylate,- allylmethacrylate, diethyl iumara'te, vinyl benzoate, to yield solutions'wjhichhrecapable of being totally'polymerized and-leavingno solvent to be evaporated." jsuchsolutibns'a're particularly useful in "applications where evaporation of a solvent'constitu'te's atechnical'or health hazard. They are likewise useful as fiuidmolding compositions capable ofbingcured'with' a minimum of shrinkage. I I

Application of heat attemperatufessuch' as 60-200 C. to compositions containing my interpolymers, particularly mtnepreeenbe of peroxidic catalysts, induces further polymerization whereby the products are "coiii rtedto an'linsoluble and essentially infusible state.- -Suitable inert addends includingdyesI- pigmentsf 'fillers and plasticizers can be incorporated with {my interpolymers; preferably at the"s'oluble," fusible stageprior'to final cure.

The fmicwmg examines in more detail. All parts "a EXAMPLE 1 To illustrate my discovery of the effect of interpolymerizable mono 2 alkenyl compounds upon the copolymerization of po1y-2-alkenyl esters with copolymerizable monoolefmic compounds, mixtures of these monomers in varying proportions are heated at 60 C. in the presence of benzoyl peroxide as polymerization promoter. In each case, the reaction is carried out until the point of incipient gelation is attained or until no 10 further increase in the viscosity of the reaction mixture is detectable.

The reaction mixtures bol appears in the Alkenyl Compounds c01- dev. mam 0 f pm m a an e fi 1 Z 9 M 6 e h k mbm M nww m -3 m mam mam dn.m a m ym mem b n u mam uha 5 1 1 mam t 0 m a oim m mum up e y mm wm m m 5m u E r e n d u emf m e lnm m D n r e a e mrm e y mmd aen.

additional interpolymerizable Z-alkenyl comtion in a minimum volume of acetone and pre- Th pound is no ducts are then dried in vacuo cipitation with the ether-hexane mixture. t at all like th a C v t onal interpolymeric pro non-polymerizable solvent in the copolymerization reaction mixture (I-ll, 28, 35, 38, 44).

Table I to constant weight.

Inter- 5 5 8 505 555 0 5 555 009.2%2037050088594520555380929073566150570013099607520777 205020077730600 1 5 2 7 5 7 9 &6 5 5Z2 4 L 60 4 2 LOWAIQZZA QWnud iiLumnmflmomomfiRrmnunmd lswl 7 7 ZLI 2 2 & 2 4% 3 1 6 3 3 11 9 21111 1% 5124 7 1Q m 1 M26 m M M7 lieactlon Peroxide Time (Hrs) polymer 1 Benzene substituted for the 2-a1keny1 alcohol or derivative. 1 No evidence ofgelation. V

Table I-Cont1nued B). (A) (G) Benzoyl Reactlon Inter- Poly-Z-Alkenyl Ester 2 91H% 91? z-Alkenyl po1 .v Pe xi T m (Hr p y 25.0 1.0 6. 2 17. 2 25. AllyLAlcohol 100. 0 l2. 0 2 84. 0 99. 0 25.0 do 136. 0 13.0 2 84.0 104:5

25.0 Crotyl Alcohol 100.0 12.0 2 84.0 .1 52.0 25. 0 1. 0 3:75 11. 6

25. 0 Methallyl chl0ride 100. 0 12. O 74. .9 88. 5

25.0 0.8 5.75 19.6 25.0 Methallyl Alcohol 100.0 8.0 41. 5 92.0

25. 0 Methallyl Ethyl Ether. 100. 0 4. 0 7. 5 5415 i 0. 25. 0 d0 200. O 5.0 33. 0 100. 0 j ethyl Fumarate.. 25.0 Methallyl Alcohol... 100. 0L 8X0 2 72. 0' 98. 5 Methyl Acrylate 25. 0 s 2. O 8175 :5 do.. 25.0 Methallyl Chloride. 10.0 2. 0.- 16. 2 4L 5 r a 25.0 -do 100.0 5.0 43:0 77.5 25.0 Y 0.8 '1.0 16.0: 25.0 100.1) l 8. 0 42.75 99; 0 V 25. 0 100.0 8. 2 72. 0 77. 5"

25. 0 100. 0- 8:0 z 7210 I 108. 0 25. 0 Y 2. 0 5.5 17.0 25. 0 Allyl Alcohol 100.0 13.5 i 1 76. 5" 35. 6 25. 0 Methallyl Alcohol 100. 0. 10. 0 2 82. 5 37. 3

25. 0. Methallyl Ethyl Ether. 100.0; 10. 0-; 2 82. 5 112. 5

25. 0 Methallyl Acetate... 100.0 10.0 23; 9 79.0

25. 0 Methallyl AlcohoL. 100. 0 8. 0 2 72.0 V 62. 0 25. 0 Methallyl Chloride. 10010 4. 0 2 72. 0 75. 5 .25. 0 Methallyl Ethyl Ether 100. 0" 4. 0 1 10.75 6555 25. 0 Methallyl Acetateninfi 100 0 8. 0 2 72.0. 63. 5

25. 0 Methallyl Alcohol. 100. 0 8.0 2 72. 0 69.0

25.0 Methallyl Chloride 1000 1 i 8.0 1 72. 0. 83. s

25 0 MethallylEthyI Eth 100. 0 4:0 10. 75 73. 0

25. 0 Mothallyl Acetate; 100; 0 8:0 1 72.0 70:5

Les

converted to the s'o1u'b1e,'"interpolymeric form. This. conversion increases,asthearnount of the monqrallienylcompound. n hef ea tant. m xt, re: is. increasechumfl, hemai n110 12959 of the oo y-zral eml est r. a i, merizable. monqo 1 om 9. vertedtothe. o uble. nt rn. la EQllQf; I1QlllliZ31iQ The chlorine content oi the product arises from the c of "t polymerized vinyltrichloro ace ate"; while the nyaroxyl groups are" derived 7' telpolyinrizefi all'fl al'qoholf Thej iodine ates the residue. un SaturatiOn' which by the'iiitei'p'olymerized hieh "availafileforfur- (b) One-half of the crude reaction mixture is poured into n-hexane and the precipitated interpolymer is further purii'ied 'by repe ted solution in fo m dmpi itati mfi hhex ne: After drying; to constant weight in vacuo, '6 3.2 parts of polymericsolidare obtained which corresponds to a total yie1d 0 f,,126 .4 parts of 11518111581 polymer from the entire reaction mixture.

AnaZysis.Found: hydroxyl content; 6.14%.; acetio'acid, 3.8%; iodir e number, 157.01; li itin viscosity [721 ina'cetohe,0, 051.

(c) The remainder of the crudereaction mixture from '(a) above is admixedjWithfZfifllParts of diethyl fumarate and evacuated at 30C. and 5 mm. pressure until distillation ceases. A's'o1u-' tion of 1.78 pa'rts'oibenzoyl peroxide in 10parts of .benzene' is added and? evacuation continued. until the benzene is removed. The residual syrup poured into a plate'mold andjcured by heating for 2.3' hours'at 45930;, 13,.2jhours' at- 90 C. and finally for2.0 hoursat 100.10. The resulting clear; colorless sheet issolve'nt-resistant and possesses a Rockwell" hardness of;L1.05j.'

EXAMPLE mixtur i -5 a ts I obiltyl n 1, pa ts of (ha-11x1 fumarate Pa ts. wns a ohol an t. o 'benzpy er x de wheel d. in a sealed vessel for 82 hours; t f C. The unreacted isobutylene isthen evaporatedat room t mpera ure. and. h isyrlmy. ee tiqe mix re. is po red nt n-hes ne, he nesi itate nterp me s ther. not es x repeat e e uli e n a ne. nd. ret pittioe wi h n-h xfje- After drying in vacuo to; constant weightl l2l9 p rt f pol mer .0 9 a e qb i'ee Analysis.--Fouhd: C, 63.97% H, 7.21%.; iodine number Wijs),1Q4. The n lysis orre pon s t e n r nternql men on ainin approx ma ely 3 y, ei mq ee r enw 9 sqbut l ei 72 diallyl fun arate and of allyl alcohol. represents a conversion of, appi-o 70%,

of the monomeric diallyl fumarate to the interpolymeric form. The iodine number indicates the large amount of residual unsaturation available in the interpolymer for further polymerization or copolymerization with reactive monomers.

(b) When the above copolymerization is repeated in the absence of the allyl alcohol, the reaction mixture gels to an insoluble mass before the copolymerization has proceeded for more than an hour. The copolymerization is again repeated in the absence of allyl alcohol but in more dilute solution by tripling the amount of isobutylene, i. e., by using 20.5 parts. However, little improvement is noticeable since gelation still occurs within approximately one hour.

Six parts of the soluble, unsaturated ternary interpolymer of isobutylene, diallyl fumarate and allyl alcohol prepared in (a) above are dissolved in 4.0 parts of styrene together with 0.012 part of benzoyl peroxide and heated in a mold for 16 hours at 60 C. and then for 2 hours at 120 C. to yield a clear, colorless casting which is substantially infusible and insoluble, and has Rockwell hardness of L88, M63, and P51. When diethyl fumarate is substituted for styrene in the above, a clear, insoluble, heat-resistant casting is securedwhich has Rockwell hardness of L112, M110, and P107.

EXAMPLE 5 A mixture of 48.2 parts of bis-(beta-chloroethyl) fumarate, 39.2 parts of diallyl fumarate, 54.0 parts of allyl alcohol and 2.98 parts of benzoyl peroxide is heated at 60 C. for 6 hours. The reaction mixture is cooled and poured into hexane and the precipitated interpolymer is further purified by repeated solution in acetone and precipitation with hexane.

After drying in vacuo to constant weight, 72 parts of polymeric solid are obtained.

Analysis.-Found: C1, 13.44%; hydroxyl content, 3.97%; iodine number (Wijs), 73.2.

The chlorine content of the product arises from the presence of interpolymerized bis(beta-chloroethyl) fumarate, while the hydroxyl groups present are derived from the interpolymerized allyl alcohol. The iodine number indicates the unsaturation present which resides in the interpolymerized diallyl fumarate.

Upon heating a sample of the interpolymer at elevated temperatures, it is converted to an insoluble, infusible product.

EXAL/[PLE 6 AnaZysis.Found: hydroxyl content, 2.74%; iodine number, 88.9.

Seven parts of the interpolymer are dissolved in 3 parts of diallyl adipate together with 0.5 parts of benzoyl peroxide, and the mixture is cured in a cylindrical mold by heating for 19 hours at 60 C. and then for 2 hours at 90 C.to give a clear, hard, solvent-resistant plug.

(0) The remainder of the crude copolymerization reaction mixture from (a) above is admixed with 56.4 parts of diethyl fumarate and evacuated at 30 C. and 5 mm. until distillation ceases. A solution of 3.94 parts of benzoyl peroxide in 23.4 parts of benzene is then added and evacuation continued until the benzene is removed. The residual syrupis poured into a plate mold and cured by heating for 16.3 hours at C. and then for 2.4 hours at 90 C. The resulting clear, colorless and solvent-resistant sheet has Rockwellhardnesses of L101 and M81.

EXAMPLE '7 Twenty-five and five tenths parts of bis-betachloroethyl itaconate are mixed with 19.6 parts of diallyl fumarate, 18.0 parts of allyl alcohol and 2.423 parts of benzoyl peroxide and the mixture is heated at 60 C. for 5 hours. The reaction mixture is cooled, poured into n-hexane, and the precipitated interpolymer is further purified by repeated solution in acetone and precipitation with hexane. After drying in vacuo to constant weight, 25.7 parts of polymeric solid are obtained.

Analysis. Found: chlorine, 13.39 iodine number (Wijs), 67.5; hydroxyl content, 2.05%.

The chlorine content of the interpolymer indicates the presence of interpolymerized bis-betachloroethyl itaconate. The hydroxyl content arisesfrom the presence of interpolymerized allyl alcohol, and the iodine number reveals the residual unsaturation in the interpolymer which is derived from the interpolymerized diallyl fumarate and which is available for further polymerization.

EXAMPLE 8 (a) A mixture of 78.5 parts of diallyl fumarate, 197.2 parts of methallyl alcohol, 31.0 parts of dimethyl itaconate, and 12.4 parts of a 60% solution of tertiary-butyl hydrogen peroxide is heated at approximately 110 C. for 24 hours. One-half of the reaction mixture is subjected to the same isolation and purification procedure as in previous examples and yields 62.5 parts of polymericsolid which corresponds to a total of 125 partsfrom the entire reaction mixture.

AnaZysis.Found: hydroxyl content, 2.77%; iodine number, 93.2.

(b) Five parts of the interpolymer are dissolved in a mixture of 4 parts of xylene, 1 part of nbutanol, and 0.1 part of cyclohexanone, and after the solution is flowed out into a glass panel, it is cured by baking for 1 hour at 100 C. to yield a clear, colorless film which is insoluble in acetone.

(0) Seven parts of the interpolymer are dissolved in 3.0 parts of n-butyl acrylate together with,0.07 part of benzoyl peroxide and cured by heating in a coverless mold at C. After heating for 18 minutes in the presence of air, the resulting casting is tack-free and resistant to attack by organic solvents. Moreover, it is not discolored even after being heated for 25 hours at 90 C.

(d) The remaining half of the original crude copolymerization reaction mixture prepared in (a) above, is admixed with 29.2 parts of diethyl fumarate and evacuated at room temperature and 5 mm. pressure to a thick syrup. A solution of 1.285 parts of benzoyl peroxide in 15 parts of benzene is then added and evacuation continued until distillation ceases. The residual syrup is poured into a plate mold and cured by heating 13. for 16 hours at 60 .0. .and{'f or-.-2= additional hours at 90 C. The resulting clear, colorless sheet possesses good dimensional stability and solvent resistance and has Rockwell hardnesses '0fa1i94; M73 andfP585 EXAMPLE-9- AH: mixtures: of 9:81: parts; of diallyl fumaratm; 15.90 .-parts:.oft; allylpalcohol, 6.73 .parts of-beta. chloroethyl acrylate and 0.888 part of benzoylperoxideiislheated; for: 3:5.;;hours. at 60? The reactiommixtureyis scooledwand ;poured:;intoj,;hex-

ane: aftersiwhichzthe precipitated interpolymc is;

further purifiedfhwrepeated:isolution inacetone and'iprecipitationa;with-.hexane; Uponzdrying in vacuoito constant sweight iv =.4;;parts.-,ofapoly nericr solid are obtained.

Analy is.-.-Found: Cl. 8.99%; hydroxyl' content, 3.43%; ,iodinenumb'er (Wijs) 82.6.

The-chlorinecontent: of'theproduct arises from the presence of interpolymerized beta-chloroethyl acrylate, While the hydroxyl groups present are derived from the interpolymerized allyl alcohol. The iodine-number-indicates =the'unsatjuration presentwhich resides inthe interpplymerized diallyl fumarate.

Upon" Heating a sample --of the interpolymer- -at elevated" temperatures, itis converted to an in-- soluble infusible product;

EXAMPLE 10-.

AnaZysis.-Found': iodine number, 133.8:

Upon, heating a'sample-off the interpolymerat elevated temperatures, it-is converted to -animsoluble; inf usible mass.-

Fourteen parts of interpolymer 10-h. are dissolved in 6 parts of n-butyl acrylate together with 0.14 part of benzoyl peroxide and the mixture is cured in a mold by heating at 60 C. for 46.6 hours. The resulting casting is colorless and solventresistant.

(c) The remainder of the crude interpolymerization reaction mixture from 10-11 above is admixed with 27.8 parts of diethyl fumarate and evacuated as in previous examples. Upon heating with 1.6 parts of benzoyl peroxide in a plate mold for 15.4 hours at 60 C. and then for 2.0 hours at 90 C., a clear, colorless sheet is obtained which has a Rockwell hardness of M74.

EXAMPLE 11 A mixture of 30.0 parts of'vinyl chloride, 23.5 parts of diallyl fumarate, 36.2 parts of methallyl chloride and 1.21 parts of benzoyl peroxide is heated at 60 C. for 24.25 hours. The reaction mixture is cooled and poured into n-hexane after which the precipitated interpolymer is further purified by repeated solution in acetone and precipitation with n-hexane. Upon drying the product in vacuo to constant weight, 31.2 parts of and-$2.3. .%;i:. I1 lh1QIi Q- he odin umb indicates the large amount of "residual unsatura time mm. nte e rner. which. s. av il b e for further pol 'nierization P nl catinee mime, 'e -slinolym r er i dx smperaturss. itis llo tlx oii rtedt e nseleb eme s- I asmlxtmreeora 2=5,;na ts-0t nxlichleridae tend a tso e gri s ide s new edaa. 2:60 .forfli); I is cooled and evacuated at and 5 mm. pressure to .a viscous syrup. The latter is poured into-n-hexane and the precipitated interpolyimeis isspurifiedzz by-mcmated solution; in

acetone andiprecipitationawitlia.neliexane. Aiter drying; inmvacuoetd.constant:weight; 42. -par-ts of polymericsolideareobtained:

(a) Th1'ee -and.=.five. tenths .:parts of the interpolymer: are-: dissolved; in: 125;: parts-.5 of diethyl fumarate; together" withi0;03.-part;ofibenzoyl peroxide; and the .nnxturex isscurech a..cylindrical mold-a by h'eating for. 9flfihou-rssat 60.2: C; The-.resuiting; colorless transparentz. plug is; solventresiste'me' and 31121852: Rockwell hardness. of L54.

(b) When: Example 12 a. -v i'ss repeatediwith. diallyl fumarate substituted for di'ethyllfumarate, the resulting-colorless;product has a, hardness of 15106;".

. mix ure: on 215 partsmf-s vinx1ich10ride...3-9..2 partsqof; diailyl; furnarate; 44. .4. parts cf; 2.;-,chl01,'o: allyl'l chloride laze ioholornn nener2;), nd; L94 parts-gofibenzoylperoxideds heatedzatzGO .C: for 29.5 hours, and after isolating-rand:purifying. the reaction product: as in- Example. 3; above, 42.5 parts-of white-.polymericz-solidgare obtainediwhich iszsolublezinzacetone; chloroform. ethyLacetate benzenezandixxlenez (a) Ten parts of the intcrpolymer are dissolved in 4.5 parts of diethyl fumarate together with 0.09 part of benzoyl peroxide. The mixture is poured into a mold and cured by heating for 15 hours at 60 C., followed by 3 hours at C., and finally for 2 hours at C. The resulting transparent product is solvent-resistant and has a Rockwell hardness of L70. It undergoes no appreciable distortion at 120 C. and is completely non-flammable, i. e., it will not support combustion.

EXAMPLE 14 A mixture of 19.4 parts of vinylidene chloride, 19.6 parts of diallyl fumarate, 45.3 parts of methallyl chloride and 3.9 parts of benzoyl peroxide is heated in a sealed vessel at 60 C. for 169 hours. The clear, somewhat viscous reaction mixture is poured into n-hexane and the precipitated interpolymer is further purified by solution in acetone and precipitation with gasoline. After drying in vacuo to constant weight, 44.8 parts of polymeric solid are obtained.

Analysis.-Found: C, 48.5%; H, 5.50%; C1, 33.60%; iodine number, 67.7.

polymen-i i lid-er bti QdMbiQh ss lubl i n.

f ."me a lyl? h o de te. fisi ar me hellyiz The analysis corresponds to a ternary interpolymer containing approximately 38.4% by weight of diallyl fumarate, 27.5% of vinylidene chloride and 35.4% of methallyl chloride. This corresponds to a conversion of approximately 88% of the monomeric diallyl fumarate to the interpolymeric form. The iodine numberindicates the amount of residual unsaturation in the interpolymer which is available for further polymerization.

(a) Three and five-tenths parts of the interpolymer are dissolved in 1.5 parts of diethyl fumarate together with 0.03 part of benzoyl peroxide and the solution is cured by heating in a mold for 48 hours at 60 C. and then 1 hour at 120 C. The resulting product is substantially insoluble and infusible.

(5) Example 14-a is repeated using monomeric diallyl fumarate in place of diethyl fumarate. The molded product has a Rockwell hardness of L105 and is insoluble in acetone, chloroform and benzene.

EXAMPLE 15 Nineteen and four-tenths parts of vinylidene chloride, 39.2 parts of diallyl fumarate, 44.4 parts of 2-chioroallyl chloride (2,3-dichloropropene) and 1.936 parts of benzoyl peroxide are mixed and heated at 60 C. for hours. The reaction product is isolated and purified as in Example 2 and amounts to 52.3 parts of white polymeric solid which is soluble in acetone, chloroform, ethyl acetate, benzene and xylene. Upon heating a sample of the interpolymer at elevated temperatures it shortly becomes converted to an insoluble, infusible state. support combustion.

(a) Ten parts of the soluble interpolymer are dissolved in 4.5 parts of n-butyl acrylate together with 0.09 part of benzoyl peroxide, and the mixture is cured in a cylindrical mold by heating at C. for 15 hours, and then for 3 hours at 90 C. The resulting transparent plug is unattached by common solvents, it is self-extinguishing (i. 6., it will not support combustion), and it has a Rockwell hardness of L50.

(1)) When Example 15-11. is repeated with the substitution of diethyl fumarate for the n-butyl acrylate, a solventand flame-resistant product is obtained having a Rockwell hardness of L81.

This product will not EXAMPLE 16 A mixture of 14.6 parts of vinylidene chloride, 29.4 parts of diallyl fumarate, 87.5 parts of a mixture of isomeric dichlorobutenes believed to consist chiefly of 2-chloromethallyl chloride, and 2.42 parts of benzoyl peroxide is heated at C. for 100 hours. After the usual isolation and purification, 483 parts of solid interpolymer are obtained.

Ten parts of the interpolymer are dissolved in 4.5 parts of diethyl iumarate together with 0.09 part of benzoyl peroxide. The mixture is cured by heating in a mold for 15 hours at 60 C. and then for 3 hours at C. to yield an insoluble casting. This casting does not support combustion.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A soluble, unsaturated, ternary interpolymer derived from a monomeric mix containing, as the sole monomers, one molar equivalent of diallyl fumarate, from 0.1 to 8 molar equivalents of vinylidene chloride and from 0.2 to 15 molar equivalents of a Z-alkenyl chloride selected from the group consisting of allyl chloride and methallyl chloride.

2. The method of preparing a soluble, unsaturated, ternary interpolymer from a monomeric mixture of one molar equivalent of diallyl fumarate and from 0.1 to 8 molar equivalents of vinylidene chloride, which comprises carrying out the said interpolymerization in the presence of frorrr 0.2 to 15 molar equivalents of a Z-alkenyl chloride selected from the group consisting of allyl chloride and methallyl chloride, the said monomers being the sole monomers :present.

PLINY O. TAVvNEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. A SOLUBLE, UNSATURATED, TERNARY INTERPOLYMER DERIVED FROM A MONOMERIC MIX CONTAINING, AS THE SOLE MONOMERS, ONE MOLAR EQUIVALENT OF DIALLYL FUMARATE, FROM 0.1 TO 8 MOLAR EQUIVALENTS OF VINYLIDENE CHLORIDE AND FROM 0.2 TO 15 MOLAR EQUIVALENTS OF A 2-ALKENYL CHLORIDE SELECTED FROM THE GROUP CONSISTING OF ALLYL CHLORIDE AND METHALLYL CHLORIDE. 